Hair cosmetic compositions

ABSTRACT

A hair care composition comprising: (a) from about 0.01 to about 3% by weight of gelling agent comprising a copolymer of methyl vinyl ether/maleic anhydride, cross-linked with C 4  -C 16  alkadiene of hydrolysis products thereof; (b) from about 0.1% to about 10% by weight of hair fixative copolymer comprising a cationic copolymer of nonionic cellulose and diallyl dimethyl ammonium chloride; and the balance comprising a carrier suitable for application to hair. The liquid hair cosmetic products have an improved non-tacky on-hair and on-hand feel, demonstrate excellent hair styling benefits in addition to ease of brush-out.

TECHNICAL FIELD

The present invention relates to hair cosmetic compositions. Moreparticularly, this invention relates to hair cosmetic compositionscontaining a gelling agent and a hair fixative/conditioning polymer andhaving improved "in-use" and "on-hair" feel properties in addition tomanageability and style retention benefits.

BACKGROUND OF THE INVENTION

The desire to have the hair retain a particular shape is widely held. Acommon methodology for accomplishing this is applying hair styling, or"setting" compositions to the hair, typically to damp or dry hair. Thesecompositions provide temporary setting benefits, and should be removableby water and/or by shampooing. The materials used in the compositions toprovide the setting benefits are generally applied in the form ofmousses, gels, lotions or sprays.

High levels of style retention, or hold, are typically expected fromhair compositions whether applied as a gel or a spray. Style retentionin gel products is typically achieved by use of one or more hairfixative polymers, such as polyvinylpyrollidone (PVP) and the copolymerof PVP with vinyl acetate (PVP/VA) in combination with a gelling agent.A commonly used gelling agent is crosslinked polyacrylic acid, known bythe CTFA name of Carbomer. When such polymers are incorporated into hairfixative compositions containing conventional gelling agents they canprovide suitable style retention attributes. However, such compositionscan give a sticky feel on the hair and hands during and afterapplication as well as leaving the hair feeling stiff and unnatural.

It has now been found that certain combinations of gelling agents andhair fixative polymers can deliver excellent styling benefits withoutthe sticky and stiff feel usually associated with conventional stylinggels.

Thus a need exists for hair styling compositions which deliver effectivestyle retention, impart a hair conditioning effect, have a non-stickyhair and on-hand feel, are easily brushed out, are resistant toflakiness and at the same time have stable product and viscositycharacteristics and remain fully stable under long term and stressedtemperature storage.

SUMMARY OF THE INVENTION

According to one aspect of the invention, there is provided a haircosmetic composition comprising:

(a) from about 0.01% to about 3% by weight of gelling agent comprising acopolymer of methyl vinyl ether/maleic anhydride, crosslinked with C₄-C₁₆ alkadiene or hydrolysis products thereof;

(b) from about 0.1% to about 10% by weight of hair fixative polymercomprising a cationic copolymer of nonionic cellulose and diallyldimethyl ammonium chloride; and

(c) the balance comprising a carrier suitable for application to hair.

The essential, as well as the optional, components of the presentinvention are described below. All levels and ratios are on a weightbasis unless otherwise specified.

Gelling Agent

The compositions of the present invention contain from about 0.01% toabout 3% preferably from about 0.05% to about 2%, more preferably fromabout 0.5% to about 1.5%, most preferably from about 0.6% to about 1% byweight of gelling agent. It is this gelling agent which in combinationwith a cationic hair fixative polymer imparts hair setting andconditioning benefits without the tacky dry-hair feel and on-handstickiness normally associated with hair styling cosmetics. The gellingagents suitable for use in the present invention comprise a copolymer ofmethyl vinyl ether/maleic anhydride, and hydrolysis products thereof,crosslinked with C₄ -C₁₆, preferably C₆ -C₁₂, more preferably C₈ -C₁₀alkadiene. The gelling agents typically have a viscosity in the regionof from about 50,000 cps to about 150,000 cps, preferably from about70,000 cps to about 100,000 cps (measured as 0.5% gelling agent innon-alcoholic solution at pH7; Brookfield RVT, Spindle TE, 10 rpm).

In its broadest aspect, the copolymer utilised in the presentapplication comprise a copolymer of methyl vinyl ether/maleic anhydride(hereafter identified as A) crosslinked with C₄ -C₁₆, preferably C₆-C₁₂, more preferably C₈ -C₁₀ alkadiene (hereafter identified as B).Examples of suitable polymers and their preparations are described indetail in "Polymers and Thickeners" Vol. 108, May 1993, p61-67, S. L.Kopolow, Y. T. Kwak and M. Helioff. These polymers comprise part A and Bas defined above. In preferred embodiments, B comprises C₆ -C₁₄alkadiene, more preferably a C₆ -C₁₂ alkadiene, most preferably a C₈-C₁₀ alkadiene.

The preferred gelling agent for use herein is methyl vinyl ether/maleicanhydride, crosslinked with 1,9-decadiene (PVM/MA decadienecrosspolymer), available from ISP as Stabileze 06 (RTM).

The hair gelling agents, herein are preferably utilised in at leastpartially neutralised form in order to obtain the required gel structureand overall pH of the hair cosmetic compositions.

The gelling agent can be neutralised to a level of from about 30% toabout 100%, preferably from about 40% to about 98%, more preferably fromabout 50% to about 95% with base. Any conventionally used base, organicor inorganic, may be used for neutralisation of the acidic gellingagents. Hydroxides of alkali and alkaline earth metals and aminoalcohols are suitable neutralisers for use in the present hair cosmeticcompositions.

Examples of suitable organic neutralising agents which may be includedin the hair cosmetic compositions of the present invention includeamines, especially amino alcohols such as2-amino-2-methyl-1,3-propanediol (AMPD), 2-amine-2-ethyl-1,3-propanediol(AEPD), 2-amino-2-methyl-1-propanol (AMP), 2-amino-1-butanol (AB),monethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA),monoisopropanolamine (MIPA), diisopropanolamine (DIPA),triisopropanolamine (TIPA), dimethyl steramine (DMS) and amino methylpropanol (AMP) and mixtures thereof.

Preferred neutralising agents for use in compositions of the presentinvention are potassium and sodium hydroxides, aminomethyl propanol(AMP) and triethanolamine (TEA) and mixtures thereof.

In addition to the specific gelling agents as detailed supra suchcompositions may optionally include an auxiliary gelling agent at fromabout 0.01% to about 1%, preferqably from about 0.1% to about 0.5% byweight. Suitable auxiliary gelling agents can be selected from anyconventional gelling agent such as a crosslinked polyacrylic acidcopolymer, ethylene maleic anhydride copolymers or hydroxyethylcelluloseand its derivatives. The preferred auxiliary gelling for use herein ishydroxyethylcellulose.

Carrier

The hair cosmetic compositions of the present invention also include acarrier which can be aqueouse or non-aqueous and mixtures thereof. Thiscan comprise any of those conventionally used in polymer containing haircosmetic formulations. The carrier is generally present in the haircosmetic compositions at from about 70% to about 99.89%, preferably fromabout 78% to about 99.5% by weight. More preferably, the carrier ispresent at from about 80% to about 99% by weight of the totalcomposition.

Organic solvents suitable for use in the carrier in compositionsaccording to the present invention include C₁ -C₆ alkanols, carbitol,acetone and mixtures thereof. C₁ -C₆ alkanols preferred for use in thepresent compositions are C₂ -C₄ monohydric alcohols such as ethanol,isopropanol and mixtures thereof.

The preferred hair compositions according to the present inventioncontain from 70% to about 99.89% by weight of water, preferably from 78%to about 99.5%, more preferably from about 80% to about 99% by weight ofwater as the carrier.

Cationic Hair Fixative Polymer

In addition to the gelling agent the compositions according to thepresent invention comprise, as a second essential component, a hairfixative polymer. This hair fixative polymer is preferably solubilizedor colloidally dispersed in the hair cosmetic carrier along with thegelling agent copolymer.

The preferred hair fixative polymer component of the hair cosmeticcompositions of the present invention comprises a cationic copolymer ofhydroxyethyl cellulose and diallyl dimethyl ammonium chloride which isknown by the CTFA name Polyquaternium 4 and marketed under the tradenames Celquat L200 (RTM) and Celquat H100 (RTM) by National Starch andChemical Ltd.

The hair fixative polymer is present in an amount of from about 0.1% toabout 10%, preferably from about 0.3% to about 8%, more preferably fromabout 0.5% to about 6%, most preferably from about 0.8% to about 3% byweight of composition. In compositions according to the presentinvention the weight ratio of gelling agent: hair fixative polymer is inthe range of from about 10:1 to about 1:10.

Other hair fixative polymers suitable for use herein in conjunction withthe above material include any polymer which is soluble or colloidallydispersible in the hair cosmetic carrier. Solubility and dispersibilityare determined at ambient conditions of temperature and pressure (25° C.and at 101.3 kPa (1 Atm)). Such copolymers may be cationic or nonionicin character. Copolymers suitable for use herein have a molecular weightin the range of from about 1,000 to about 5,000,000, preferably fromabout 50,000 to about 4,000,000, more preferably from about 100,000 toabout 3,000,000, most preferably from about 500,000 to about 2,000,000.

In addition cationic and nonionic resins may be utilised as detailedbelow. Polycationic hair conditioning polymer resins suitable for useherein are described below. For convenience in describing the polymershereof, monomeric units present in the polymers may be referred to asthe monomers from which they can be derived. The cationic monomers canbe derived from polymerizable cationic starting monomers, or frompolymerizable nonionic monomers which are modified subsequent topolymerization to be of cationic character.

These cationic unsaturated monomers can be polymerized in cationic form,or as an alternative they can be polymerized in-the form of theirprecursors, which are then modified to be cationic, for example, by aquaternizing agent (eg. ethyl monochloroacetate, diemethyl sulfate,etc.). Preferred cationic monomers include dimethylaminoethylmethacrylate, quaternized dimethylaminoethyl methacrylate,diallyldimethyl ammonium chloride, vinylimidazolium quaternary ammoniummonomers and mixtures thereof.

Respresentative examples of nonionic monomers are acrylic or methacrylicacid esters of C1-C24 alcohols, such as methanol, ethanol, 1-propanol,2-propanol, 1-butanol, 2-methyl-1-propanol, 1-pentanol, 2-pentanol,3-pentanol, 2-methyl-1-butanol, 1-methyl-1-butanol, 3-methyl-1-butanol,1-methyl-1-pentanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol,t-butaonl, cyclohexanol, 2-ethyl-1-butanol, 3-heptanol, benzyl alcohol,2-octanol, 6-methyl-1-heptanol, 2-ethyl-1-hexanol,3,5-dimethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, 1-decanol,1-dodecanol, 1-hexadecanol, 1-octadecanol, and the like, the alcoholshaving from about 1-24 preferably from about 4-18, more preferably fromabout 4-12 carbon atoms; styrene; chlorostyrene; vinyl estes such asvinyl acetate; vinyl chloride; vinylidene chloride; acrylonitrile;alpha-methylstyrene; t-butylstyrene; butadiene; cyclohexadiene;ethylene; propylene; vinyl toluene; alkoxyalkyl (meth)acrylate, such asmethoxy ethyl (meth)acrylate and butoxytheyl (meth)acrylate; andmixtures thereof. Other nonionic monomers include acrylate andmethacrylate derivatives such as allyl acrylate and methacrylate,cyclohexyl acrylate and methacrylate, oleyl acrylate and methacrylate,benzyl acrylate and methacylate, tetrahydrofurfuryl acrylate andmethacrylate, ethylene glycol di-acrylate and -methacrylate,1,3-butyleneglycol di-acrylate and -methacrylate, diacetonacylamide,isobornyl (meth)acrylate, and the like.

Preferred nonionic monomers include n-butyl methacrylate, isobutylmethacrylate, 2-ethylhexyl methacrylate, methyl methacrylate,t-butylacrylate, t-butylmethacrylate, and mixtures thereof.

Representative polar nonionic monomers include acrylamide,N,N-dimethylacrylamide, methacrylamide, N-t-butyl acylamide,methacrylonitrile, acrylamide, acrylate alcohols (eg. C2-C6 acrylatealcohols such as hydroxyethyl acrylate, hydroxyproxyl acrylate),hydroxyethyl methacrylate, hydroxpropyl methacrylate, vinyl pyrrolidone,vinyl ethers, such as methyl vinyl ether, acyl lactones and vinylpyridine, allyl alcohols, vinyl alcohols and vinyl caprolactam.

Preferred polycationic polymer resins for use herein include cationicguar gum, cationic polysaccharides, homopolymers of dimethyldiallylammonium chloride, copolymers of dimethyldiallyl ammonium chloride andacrylamide, cationic amino-functional homopolymers and copolymersderived from acrylic acid and/or methacrylic acid, especially fromalkylaminoalkyl acrylate and methacrylate monomers such asdimethylacmonoethyl acrylate and methacrylate, polyalkylene imines andethoxy polyalkylene imines, vinylimidazolium/vinylpyrrolidone quaternaryammonium copolymers, and mixtures thereof.

The auxilliary hair fixative polymer is incorporated with thePolyquaternium 4 at levels of from about 0.01% to about 10%, preferablyfrom about 0.15 to about 5% by weight. The combination of Polyquat 4 andauxilliary hair fixative polymer is valuable for providing overall hairfeel benefits, particularity with respect to flakiness.

The present compositions can be formulated as leave-in hair cosmeticcompositions such as gels or creams. Methods of making the hair cosmeticcompositions of the present invention are described more specifically inthe examples.

The hair cosmetic compositions of the present invention may contain achelating agent at a level of from about 0.01% to about 5%, preferablyfrom about 0.5% to about 3%, more preferably from about 0.08% to about1% by weight. Chelating agents suitable for the compositions accordingto the present invention include salts of ethylenediamine tetraaceticacid including ethylenediamine tetraacetic acid, disodiumethylenediamine tetraacetic acid and pentasodium pentatate. Thepreferred chelating agent for use in compositions according to thepresent invention is tetrasodium ethylenediamine tetraacetic acid.

The hair cosmetic compositions of the present invention can also containa variety of non-essential, optional components such as preservatives,surfactants, block polymers, thickeners and viscosity modifiers,electrolytes, fatty alcohols, pH adjusting agents, perfume oils; UVscreening agents; hair conditioning agents, Pearlescants, emollients;lubricants and penetrants such as various lanolin components; proteinhydrolysates and other protein derivatives; ethylene adducts andpolyoxyethylene cholesterol; volatile and non-volatile silicone fluids.Such conventional optional ingredients are well known to a personskilled in the art, e.g. surfactants used as perfume solubilizing agentssuch as anionics (e.g., sodium alkyl sulphates, nonionics (amineoxides); amphoterics (aliphatic secondary or tertiary amine derivatives)zwitterionics (aliphatic quaternary ammonium; phosphonium or sulphoniumderivatives) and fluorinated surfactants (e.g. Zonyl FSK) (RTM),preferred surfactants for use herein being nonionics such aspolyethylene glycol fatty acid esters, isosteareth-20, polysorbate-20,PPG-12-PEG-65 lanolin oil, PEG40 hydrogenated caster oil, polysorbate80, Oleth-20 and Nonoxynol-10, thickeners and viscosity modifiers suchas diethanolamides of long chain fatty acids, sodium chloride, sodiumsulphate, and ethyl alcohol; block polymers of ethylene oxide andpropylene oxide such as Pluronic (RTM) F88 offered by BASF Wyandotte;preservatives such as DMDM hydantoin, methyl paraben, propyl paraben anddiaxolidinyl urea; fatty alcohols such as cetearyl alcohol; electrolytesuch as earth and alkaline-earth metal salts; quaternary ammonium ionsand cationic amines and halogen ions; pH adjusting agents such as citricacid, succinic acid, sodium hydroxide and triethanolamine; perfiume oilssuch as Florasynth (RTM) perfumes; hair conditioning agents such aspanthenol/pantyl B and pearlescing agents such as ethylene glycoldistearate and mica and UV screening agents such as benzophenone-4 andbenzophenone-10. Each of these optional materials can be present at alevel of from about 0.01% to about 5%, preferably from about 0.05% toabout 3%, most preferably from about 0.08% to about 1%, by weight ofcomposition.

The hair cosmetic compositions of the present invention are used inconventional ways to provide the hair styling/holding benefits of thepresent invention in combination with reduced on-hair and on-hand tack.Such methods can involve applying an effective amount of the product todry or damp hair before or after the hair is styled, or both. By"effective amount" is meant an amount sufficient to provide the hairvolume and style benefits desired considering the length and texture ofthe hair. The hair cosmetic compositions according to the presentinvention may be effectively applied to the hair using the hands, usinga comb or brush or by applying with a sponge or `wipe`.

The invention is illustrated by the following non-limiting examples.

Gelling agent--Stablileze 06 (RTM)

Neutralising agent--Triethanolamine (TEA)

Hair fixative polymer A--Polyquaternium 4 (RTM)

Hair fixative polymer B--PVP/VA

Chelating agent--tetra sodium ethylenediamine tetracetic acid EDTA (Na)₄

    ______________________________________    Examples    I          II         III    ______________________________________    Stabileze 06                0.6        0.4        0.3    Carbomer 980/201                --         0.2    TEA         0.6        0.6        0.3    Polyquat 4  1.0        0.5        1.0    PVP/VA      --         0.5        0.5    EDTA (Na)4  0.1        0.1        0.1    Ethanol     --         --         10.0    Water       To balance To balance To balance    ______________________________________

The hair cosmetic formulations are prepared by (a) dispersing thegelling agent(s) into water, allowing sufficient time for hydration ofthe gelling agent (30 minutes to 1 hour), then partially neutralisingthe gelling agent with a suitable base and (b) in a separate step,solubilising the fixative polymer(s) in water along with anynon-essential optional ingredients and the chelating agent. The premixes(a) and (b) are combined and the resulting mixture is modified to thedesired viscosity and pH characteristics using the remainder of theneutralising base.

The above compositions provide effective style retention, deliver a hairconditioning effect with low on-hand and on-hair tack.

We claim:
 1. A hair cosmetic composition comprising:(a) from about 0.01%to about 3% by weight of gelling agent comprising a copolymer of methylvinyl ether/maleic anhydride, crosslinked with C₄ -C₁₆ alkadiene orhydrolysis products thereof: (b) from about 0.1% to about 10% by weightof hair fixative polymer comprising a cationic copolymer of nonioniccellulose and diallyl dimethyl ammonium chloride; and (c) the balancecomprising a carrier suitable for application to hair.
 2. A haircosmetic composition according to claim 1 wherein the viscosity of thegelling agent at 25° C. is in the region of from about 70,000 cps toabout 100,000 cps (measured as 0.5% gelling agent in non-alcholicsolution at pH7; Brookfield RVT, Spindle TE, 10 rpm).
 3. A hair cosmeticcomposition according to claim 1 wherein the gelling agent isneutralized to a level of from about 30% to about 95%, with base.
 4. Ahair cosmetic composition according to claim 3 wherein the base isselected from alkali metal, alkaline earth metal and ammoniumhydroxides, amines and amino alcohols and mixtures thereof and inparticular is selected from triethanolamine, sodium hydroxide andmixtures thereof.
 5. A hair cosmetic composition according to claim 1wherein the weight average molecular weight of the cationic copolymer isin the range of from about 1,000 to about 5,000,000.
 6. A hair cosmeticcomposition according to claim 1 wherein the cationic copolymercomprises a copolymer of hydroxy ethyl cellulose and diallyldimethylammonium chloride.
 7. A hair cosmetic composition according to claim 1wherein the hair fixative polymer is present at a level of from about0.5% to about 8%, by weight.
 8. A hair cosmetic composition according toclaim 1 wherein the weight ratio of gelling agent: hair fixativepolymer(s) is in the range of from about 10:1 to about 1:10.
 9. A haircosmetic composition according to claim 1 wherein the carrier systemcomprises water and optionally organic solvent selected from C₁ -C₆alkanols, diols, polyols, carbitols, acetone and mixtures thereof.
 10. Ahair cosmetic composition according to claim 1 wherein the gelling agentcopolymer crosslinking agent is an alkadiene selected from C₄ -C₁₆alkadienes.
 11. A hair cosmetic composition according to claim 1 whereinthe gelling agent is a copolymer of methyl vinyl ether/maleic anhydridecrosslinked with 1,9-decadiene.
 12. A hair cosmetic compositionaccording to claim 1 wherein the level of gelling agent is from about0.6% to about 1.0% by weight.
 13. A hair cosmetic composition accordingto claim 3 wherein the gelling agent is neutralized to a level of fromabout 40% to about 80% with base.
 14. A hair cosmetic compositionaccording to claim 3 wherein the gelling agent is neutralized to a levelof from about 50% to about 60% with base.
 15. A hair cosmeticcomposition according to claim 7 wherein the hair fixative polymer ispresent at a level of from about 0.8% to about 6% by weight.
 16. A haircosmetic composition according to claim 15 wherein the hair fixativepolymer is present at a level of from about 1% to about 3% by weight.17. A hair cosmetic composition according to claim 10 the gelling agentcopolymer crosslinking agent is an alkadiene selected from C₆ -C₁₄alkadienes.
 18. A hair cosmetic composition according to claim 17wherein the gelling agent copolymer crosslinking agent is an alkadieneselected from C₆ -C₁₂ alkadienes.
 19. A hair cosmetic compositionaccording to claim 18 wherein the gelling agent copolymer crosslinkingagent is an alkadiene selected from C₈ -C₁₀ alkadiene such as1,9-decadiene.